US5070161A - Heat-latent, cationic polymerization initiator and resin compositions containing same - Google Patents
Heat-latent, cationic polymerization initiator and resin compositions containing same Download PDFInfo
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- US5070161A US5070161A US07/356,903 US35690389A US5070161A US 5070161 A US5070161 A US 5070161A US 35690389 A US35690389 A US 35690389A US 5070161 A US5070161 A US 5070161A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
- C07D213/20—Quaternary compounds thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/61—Halogen atoms or nitro radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/84—Nitriles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/08—Saturated oxiranes
- C08G65/10—Saturated oxiranes characterised by the catalysts used
- C08G65/105—Onium compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G85/00—General processes for preparing compounds provided for in this subclass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/19—Quaternary ammonium compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
Definitions
- This invention relates to a novel class of cationic polymerization initiators having a heat-latency, i.e. which are normally inactive but are capable of initiating a cationic polymerization reaction only at an elevated temperature.
- the invention also relates to heat-curable resin compositions containing these initiators which are useful for the preparation of coating, adhesive, printing ink and other compositions.
- a variety of cationic polymerization initiators are known including Friedel-Crafts catalysts such as aluminum chloride, boron trifluoride-ether complex, photo-degradable onium salts (S, Se, Te), diallyl iodonium salts and the like. These known initiators are generally not selective with respect to the reaction temperature. Therefore, an epoxy resin containing these initiators begins to cure even at room temperature.
- Japanese Laid Open Patent Application (Kokai) Nos. 37003/83 and 37004/83 disclose another type of cationic polymerization initiators. They are aliphatic or aromatic sulfonium salts capable of generating carbonium cations upon heating to an elevated temperature. Initiators of this type are known as "heat-latent cationic polymerization initiator". Cation-polymerizable resins such as epoxy resins containing the heat-latent initiator are, therefore, normally inactive but capable of curing at a temperature above the cleaving temperature of the initiator. This provides a heat-curable, one-component epoxy resin composion having a greater storage-stability and a longer pot life.
- the carbonium cations produced by the thermal cleavage of the heat-latent intiator may react with water or a hydroxy group-containing compound to generate protons which, in turn, catalyse various cross-linking reactions.
- the heat-latent cationic initiator may find uses in catalyzing the curing reaction of, for example, polyester and acrylic resins with melamine resins. This also provides systems having a greater storage stability.
- the heat latent cationic initiator thus has a number of advantages over conventional cationic initiators or proton-donating catalysts.
- the prior art sulfonium type initiators have a serious problem in that their sulfur-containing decomposition products are malodorous. This limits their uses in practice.
- the present invention provides a compound of the formula: ##STR1## wherein R 1 , R 2 , R 3 and R 4 are each H, OH, halogen, an alkyl, an alkoxy, nitro, amino, an alkylamino, an alkanoyl cyano, an alkoxycarbonyl or carbamoyl; R 5 , R 6 and R 7 are each an alkyl, an alkenyl or phenyl which may be substituted with nitro, cyano, amino, halogen, an alkyl or a dialkylamino, at least one of R 5 , R 6 and R 7 being phenyl or the substituted phenyl; M is As, Sb, B or P; X is halogen; and n equals to the valency of the element M plus one.
- the present invention provides a heat-curable resin composition comprising an amount of the above benzylpyridinium or benzylammonium compound effective to initiate the curing reaction of the composition at an elevated temperature.
- benzylpyridinium or benzylammonium compound may be utilized in any one of the following systems:
- the benzylpyridinium compound of the formula I-a: ##STR2## may be synthesized by reacting a corresponding benzyl halide of the formula II: ##STR3## with a pyridine compound III-a of the formula: ##STR4## and then reacting the resulting benzylpyridium halide with an alkali metal salt of the complex anion MXn -- to metathetically produce the compound I-a.
- the benzylammonium compound of the formula I-b: ##STR5## may be synthesized by reacting the benzyl halide (II) with a tertiary amine of the formula III-b: ##STR6## and then reacting the resulting benzylammonium halide with an alkali metal salt of the complex anion MXn -- .
- the compounds of the formula I-a or I-b are thermally cleaved at an elevated temperature to produce a benzyl cation of the formula: ##STR7## which, in turn, initiates a cationic polymerization chain reaction.
- these compounds are substantially inactive at a temperature below their cleaving points. Therefore, they find a number of valuable uses such as a hardener of one-component epoxy resins.
- Typical examples of cation-polymerizable monomers are those having a cation-polymerizable functional group such as epoxide, cyclic imine, cyclic ether cyclic ester, and other groups.
- the resin composition may comprise a cation-polymerizable oligomer and/or polymer including the same structure as the above cation-polymerizable monomer in their molecules.
- the resin composition may be of the solventless type containing the above-mentioned cation-polymerizable monomer and/or a low molecular weight-polyol as a reactive diluent, or it may contain a conventional organic solvent for adjusting its viscosity to a suitable range for application.
- Typical examples of cation-polymerizable resins are epoxy resins including bisphenol A--, bisphenol S-- and bisphenol F epoxy resins; novolac type epoxy resins; diglycidyl ethers of glycols such as butanediol, hexanediol and hydrogenated bisphenol A; diglycidyl ethers of polyoxyalkylene glycols such as plyethylene glycol, polypropylene glycol and bisphenol A-alkylene oxide adducts; diglycidyl esters of dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid and adipic acid; and glycidyl ether-esters of hydroxycaboxylic acids such as p- and m-hydroxybenzoic acids.
- epoxy resins including bisphenol A--, bisphenol S-- and bisphenol F epoxy resins; novolac type epoxy resins; diglycidyl ethers of glycols such as but
- epoxide group-containing acrylic resins are also included in examples of preferred cation-polymerizable resins. These acrylic resins are produced by polymerizing a monomer mixture of glycidyl (meth)acrylate with a (meth)acrylic acid ester such as methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate and 2-hydroxyethyl (meth)acrylate optionally containing other comonomers such as styrene or its derivatives, acrylonitrile, vinyl acetate and the like.
- a monomer mixture of glycidyl (meth)acrylate with a (meth)acrylic acid ester such as methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate and 2-hydroxyethyl (meth)acrylate optionally containing other comonomers such as styrene or its derivatives, acryl
- Examples of usable polyols include low molecular weight-polyols such as ethylene glycol, propylene glycol, tetrramethylene glycol, diethylene glycol, glycerine, trimethylolpropane and pentaerythritol. It should be noted that these low molecular weight-polyols produce H + through a chain transfer reaction causing unwanted reactions of cation-polymerizable functional groups. This often results in a cured resin having a low average molecule weight and thus poor mechanical properties. Accordingly, it is more preferable to use an oligomer polyol such as polyether polyols, polycaprolactone polyol, polyester polyols and acryl polyols.
- an oligomer polyol such as polyether polyols, polycaprolactone polyol, polyester polyols and acryl polyols.
- polyols may be added to the resin composition in such an amount that their hydroxy function is 1 to 100 mole precent relative to the cation-polymerizable functional group. If the amount of polyol is too low, it is difficult to adjust the curing temperature of the resulting composition in a suitable range and the composition is not high solids. Conversely, excessive use of polyols adversely affects the curability of the entire composition.
- composition of this invention contains from 0.01 to 10%, preferably from 0.05 to 5% by weight of the resin solid content of the initiator compound of the formula I-a or I-b. If the amount of the initiator is deficient, the curability of the composition is not satisfactory. Conversely, excessive use of the initiator adversely affects the physical properties of cured composition, such as dark appearance and decreased water resistance.
- composition may contain conventional additives such as pigments, fillers and the like depending upon its intended use.
- the resulting composition may be provided as the high solids or solventless type and has an increased storage stability at room temperature although curable at a temperature above the cleaving point of the initiator.
- compositions usually contain a proton-donor such as p-toluenesulfonic acid for catalyzing the cross-linking reaction with the melamine resin. Since the addition of a free acid to the composition tends to cause gelling of the entire composition upon storage, the catalyst is blocked partially or totally in its acid function with an amine which is volatile at the curing temperature of the composition. However, the curability of this type of composition is generally not compatible with the storage stability thereof.
- a proton-donor such as p-toluenesulfonic acid
- the use of the cationic polymerization initiator of the present invention overcomes this problem.
- the initiator is substantially inactive until a critical temperature is reached.
- a carbonium cation is liberated from the initiator upon heating to a predetermined temperature and a proton is generated by the reaction of the carbonium cation with water or a hydroxy group-containing compound contained in the composition. This enables for the curability and storage stability of the composition to be compatible.
- film-forming resins are used in the coating industry in combination with a melamine resin.
- Various film-forming resins include polyester resins, polylactone resins, epoxy resins, acrylic resins and the like.
- Polyester resins are prepared by the condensation reaction of a polycarboxylic acid or its anhydride with a polyhydric alcohol. Any polyester resin having a hydroxy function at the terminal and/or middle of the polyester chain may be cross-linked with the melamine resin.
- Hydroxy terminated polylactone resins may also be cross-linked with the melamine resin.
- Epoxy resins having an epoxide function and a hydroxy function at the terminal and the middle of the molecule respectively such as bisphenol epoxy resins and novolac epoxy resins may be used in combination with the melamine resin.
- Acrylic resins containing a plurality of hydroxy functions may be prepared by copolymerizing a hydroxy group-containing acrylic monomer such as 2-hydroxyethyl (meth)acrylate with one or more comonomers such as alkyl (meth)acrylates, e.g. methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate and 2-ethylhexyl (meth)acrylate; styrene or its derivatives; (meth)acrylonitrile; vinyl acetate and the like.
- a hydroxy group-containing acrylic monomer such as 2-hydroxyethyl (meth)acrylate
- one or more comonomers such as alkyl (meth)acrylates, e.g. methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate and 2-ethylhexyl (meth)acrylate; styrene or
- Melamine resins are prepared by reacting a triazine compound such as melamine, acetoquanamine or benzoguanamine with formaldehyde, and optionally etherifying the methylol function of the resulting condensate partially or totally with a lower alkanol such as methanol or butanol.
- Thermosetting resin compositions comprising a hydroxy group-containing, film-forming resin and a melamine resin are well-known in the coating industry. Except for the use of the above-discussed cationic polymerization initiator, the composition of the present invention may be otherwise identical to these known compositions.
- the weight ratio of the hydroxy group-containing, film-forming resin to the melamine resin ranges between 50:50 to 95:5 on the solid content basis.
- composition of this invention contains from 0.01 to 10%, preferably from 0.05 to 5% by weight of the resin solid content of the initiator of the formula I-a or I-b. If the amount of the initiator is deficient, the curability of the composition is not satisfactory. Conversely, excessive use of the intiator adversely affects the physical properties of cured composition such as dark appearance and decreased water resistance.
- composition may contain convenational additives such as pigments, fillers and the like depending upon its intended use.
- Japanese Patent Publication No. 33512/88 discloses a curable resin composition containing a vinyl polymer having a plurality of alkoxysilyl group-containing side chains, a polyhydroxy compound and a curing catalyst. It is believed that the composition cures through a self-condensation reaction between two alkoxysilyl groups:
- a variety of catalysts are disclosed as being capable of catalyzing the above reactions. These include amines such as butylamine, dibutylamine, t-butylamine, ethylenediamine and the like; organic metal compounds such as tetraisopropyl titanate, tetrabutyl titanate, tin octate, lead octate, zinc octate, calcium octate, dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate and the like; and acid catalysts such as p-toluenesulfonic acid, trichloroacetic acid and the like.
- the composition containing these catalysts is curable at room temperature.
- the composition cannot be stored for a long period of time while containing the curing catalyst.
- long term storage it is necessary to store the catalyst and the resin component separately and mix the two components immediately prior to use. This is inconvenient in practice and requires to use within a pot life.
- Other approach includes to reduce the amount of catalyst and blocking the amine or acid catalyst with a suitable acid or amine. Unfortunately they all have been proven unsatisfactory in terms of film properties, storage stabilities and the like.
- the use of the cationic polymerization initiator of the present invention in the above-mentioned system overcomes these problems.
- film-forming resins containing a plurality of alkoxysilyl groups include the following:
- a monomer having both an ethylenically unsaturated function and an alkoxysilyl function in the molecule forms a homopolymer or copolymer containing a plurality of alkoxysilyl groups by itself or with acrylic and/or other comonomers.
- a first class of such monomers are alkoxysilylalkyl esters of acrylic or methacrylic acid of the formula: ##STR8## wherein R is H or CH 3 , R' and R" are each alkyl, x is an integer, and n is 0, 1 or 2.
- a second class of said monomers are adducts of (meth)acrylic acid with an epoxy group-containing alkoxysilane such as
- alkoxysilyl group-containing monomers are adducts of a hydroxylalkyl (meth)acrylate such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate with an isocyanotoalkylalkoxysilane of the formula:
- a further class of alkoxysilyl group-containing monmers are adducts of glycidyl (meth)acrylate with an aminoalkylalkoxysilane such as
- Acrylic and/or other comonomers which may be copolymerized with the alkoxylsilyl group-containing monomer include alkyl (meth)acrylates, (meth)acrylic acid, (meth)acrylonitrile, (meth)arylamide, styrene, vinyl chloride, vinyl acetate and the like.
- aminoalkylalkoxysilanes used for preparing an adduct with glycidyl (meth)acrylate may be reacted with an epoxy resin to produce a modified epoxy resin having a plurality of alkoxysilyl groups.
- Polyester resins having a plurality of free carboxyl groups may be modified with the above-mentioned epoxy group-containing alkoxysilane to give silicon-modified polyester resins.
- Polyesters having a plurality of hydroxy groups may be reacted with the above-mentioned isocyanatoalkylalkoxysilane to give silicone-modified polyester resins.
- hydroxy group-containing resins include polyester resins, polylactone resins, epoxy resins and acrylic resins.
- Polyester resins are prepared by the condensation reaction of a polycarboxylic acid or its anhydride with a polyhydric alcohol. Any polyester resin having a hydroxy function at the terminal and/or middle of the polyester chain may be employed.
- Hydroxy terminated polylactone resins may also be employed.
- Epoxy resins having an epoxide function and a hydroxy function at the terminal and the middle of the molecule respectively such as bisphenol epoxy resins and novolac epoxy resins may be employed.
- Acrylic resins containing a plurality of hydroxy functions may be prepared by copolymerizing a hydroxy group-containing acrylic monomer such as 2-hydroxyethyl (meth)acrylate with one or more comonomers such as alkyl (meth)acrylates, e.g. methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate and 2-ethylhexyl (meth)acrylate, styrene or its derivatives; (meth)acrylonitrile, vinyl acetate and the like.
- a hydroxy group-containing acrylic monomer such as 2-hydroxyethyl (meth)acrylate
- one or more comonomers such as alkyl (meth)acrylates, e.g. methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate and 2-ethylhexyl (meth)acrylate, styrene or
- Systems utilizing the self-condensation reaction of alkoxysilyl groups contain the above-mentioned silicon-containing resin and from 0.01 to 10%, preferably from 0.05 to 5% by weight of the resin solid content of the compound I-b.
- Systems utilizing the co-condensation of alkoxysilyl group with hydroxy group contain the above-mentioned silicon-containing resin, an amount of hydroxy group-containing resin at a molar ratio of the hydroxy group per alkoxysilyl group of 0.01 to 10%, preferably from 0.05 to 5% by weight of the resin solid content of the compound I-a or I-b.
- composition may contain conventional additives such as fillers, pigments and the like depending upon its intended use.
- the resulting composition has an increased storage stability at room temperature but curable at a temperature above the cleaving point of the compound I-a or I-b.
- the curing time may vary with the curing temperature but usually within one hour.
- a reaction vessel provided with a heater, stirrer, reflux condenser, water separator, fractional distillation column and thermometer was charged with 36 parts of hexahydrophthalic acid, 42 parts of trimethylolpropane, 50 parts of neopentyl glycol and 56 parts of 1,6-hexanediol.
- the mixture was heated to 210° C. with stirring.
- the mixture was heated to 230° C. at a constant rate over 2 hours while distilling out water formed as a by-product by the condensation reaction.
- the reaction was continued at 230° C. until an acid number of 1.0 was reached and stopped by cooling.
- the reaction mixture was heated again to 190° C.
- Acrylic resin solution A having a molecular weight of 3,500, a solution viscosity of M-N and a nonvolatile content of 60.5% was produced by solution polymerizing the following mixture at 120° C.
- Acrylic resin solution B having a molecular weight of 4,200, a solution viscosity of U-V and a nonvolatile content of 60.2% was produced from the following mixture.
- Example II-1 Analogous to Example II-1, the following mixture was solution polymerized at 120° C.
- a reaction vessel provided with a stirrer, thermometer, reflux condenser, nitrogen gas-introducing tube and dripping funnel was charged with 90 parts of SOLVESSO 100 and heated to 160° C. while introducing nitrogen gas.
- Acrylic Resin E was prepared from the following monomer mixture:
- Acrylic Resin F was prepared from the following monomer mixture:
- a reaction vessed used in Example II-5 was charged with 45 parts of xylene and heated to 130° C. while introducing nitrogen gas. To the vessel was added dropwise a mixture of 50 parts of ⁇ -methacryloyloxypropyltrimethoxysilane and 4 parts of t-butylperoxy-2-ethyl-hexanoate at a constant rate over 3 hours.
- Example II-8 Analogous to Example II-8, a mixture of 50 parts of ⁇ -methacryloyloxypropyldimethylmethoxysilane and 4 parts of t-butylperoxy-2-ethylhexanoate was polymerized to give Silicon Resin C.
- a reaction vessel provided with a stirrer, thermometer and reflux condenser was charged with 100 parts of Polyester Resin A obtained in Example I-1 and heated to 100° C. After the addition of 0.2 parts of dibutyltin dilaurate, 10 parts of KBK-9007 (chemically ⁇ -isocyanatopropyltrimethoxysilane sold by Shin-Etsu Chemical Co., Ltd.) were added dropwise at a constant rate over 30 minutes and the reaction allowed to proceed to completion for additional 1 hour. After cooling, Silicon Resin F was obtained. The adsorption of NCO group at 1720 cm -1 disappeared completely in the IR spectrometry of the resin.
- a reaction vessel provided with a stirrer, thermometer and reflux condenser was charged with 100 parts of bisphenol A diglycidyl ether and heated to 150° C. Then 100 parts of ⁇ -aminopropyltrimethoxysilane were added dropwise at a constant rate over 1 hour and allowed to react for additional 1 hour. After cooling, Silicon Resin G was obtained.
- Example III-4 Analogous to Example III-4, the following compositions were tested for the curability and storate stability. The results are also shown in Table III-4.
- Acrylic Resin A 100 parts were thoroughly mixed with 0.5 parts of 1-(p-t-butylbenzyl)-4-cyanopyridinium hexafluoroantimonate and 2.95 parts of PLACCEL 308 (trifuctional polycaprolactone polyol having a molecular weight of 860 sold by Daicel Chemical Industries, Ltd.). The mixture was cast on a tinplate and baked at 130° C. or 150° C. for 30 minutes.
- PLACCEL 308 trifuctional polycaprolactone polyol having a molecular weight of 860 sold by Daicel Chemical Industries, Ltd.
- Example IV-1 Analogous to Example IV-1, the following compositions were tested for the curability and initial viscosity. The results are also shown in Table IV-1.
- Example IV-2 Analogous to Example IV-1, the following compositions were tested for the curability, storage stability and initial viscosity. The results are shown in Table IV-2.
- PLACCEL 308 70 parts of PLACCEL 308, 30 parts of CYMEL 303 (melamine resin sold by Mitsui Toatsu Chemicals, Inc.) and 2 parts of 1-(4-methylbenzyl)-4-cyanopyridinium hexafluoroantimonate were thoroughly mixted. The mixture was cast on a tinplate and baked at 140° C. The curability and storage stability of the mixture are shown in Table V-1.
- Example V-1 Analogous to Example V-1, the following compositions were tested for the curability and storate stability. The results are shown in Table V-1.
- Example V-2 Analogous to Example V-1, the following compositions were tested for the curability and storage stability. The results are shown in Table V-2.
- Example VI-1 Analogous to Example VI-1, the following compositions were tested for the curability and storage stability. The results are shown in Table VI-1.
- Example VI-2 Analogous to Example VI-1, the following compositions were tested for the curability and storage stability. The results are shown in Table VI-2.
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- Pyridine Compounds (AREA)
Abstract
Benzyl pyridinium or ammonium salts of a non-nucleophilic anion are useful as a cationic polymerization initiator having a heat latency. A variety of resinous compositions containing this initiator is also disclosed.
Description
This invention relates to a novel class of cationic polymerization initiators having a heat-latency, i.e. which are normally inactive but are capable of initiating a cationic polymerization reaction only at an elevated temperature. The invention also relates to heat-curable resin compositions containing these initiators which are useful for the preparation of coating, adhesive, printing ink and other compositions.
A variety of cationic polymerization initiators are known including Friedel-Crafts catalysts such as aluminum chloride, boron trifluoride-ether complex, photo-degradable onium salts (S, Se, Te), diallyl iodonium salts and the like. These known initiators are generally not selective with respect to the reaction temperature. Therefore, an epoxy resin containing these initiators begins to cure even at room temperature.
Japanese Laid Open Patent Application (Kokai) Nos. 37003/83 and 37004/83 disclose another type of cationic polymerization initiators. They are aliphatic or aromatic sulfonium salts capable of generating carbonium cations upon heating to an elevated temperature. Initiators of this type are known as "heat-latent cationic polymerization initiator". Cation-polymerizable resins such as epoxy resins containing the heat-latent initiator are, therefore, normally inactive but capable of curing at a temperature above the cleaving temperature of the initiator. This provides a heat-curable, one-component epoxy resin composion having a greater storage-stability and a longer pot life.
The carbonium cations produced by the thermal cleavage of the heat-latent intiator may react with water or a hydroxy group-containing compound to generate protons which, in turn, catalyse various cross-linking reactions. Accordingly, the heat-latent cationic initiator may find uses in catalyzing the curing reaction of, for example, polyester and acrylic resins with melamine resins. This also provides systems having a greater storage stability.
The heat latent cationic initiator thus has a number of advantages over conventional cationic initiators or proton-donating catalysts. Unfortunately, the prior art sulfonium type initiators have a serious problem in that their sulfur-containing decomposition products are malodorous. This limits their uses in practice.
Accordingly, a strong need exists for a heat latent cationic polymerization initiator which obviates the above defects.
In one aspect, the present invention provides a compound of the formula: ##STR1## wherein R1, R2, R3 and R4 are each H, OH, halogen, an alkyl, an alkoxy, nitro, amino, an alkylamino, an alkanoyl cyano, an alkoxycarbonyl or carbamoyl; R5, R6 and R7 are each an alkyl, an alkenyl or phenyl which may be substituted with nitro, cyano, amino, halogen, an alkyl or a dialkylamino, at least one of R5, R6 and R7 being phenyl or the substituted phenyl; M is As, Sb, B or P; X is halogen; and n equals to the valency of the element M plus one.
In another aspect, the present invention provides a heat-curable resin composition comprising an amount of the above benzylpyridinium or benzylammonium compound effective to initiate the curing reaction of the composition at an elevated temperature.
The above benzylpyridinium or benzylammonium compound may be utilized in any one of the following systems:
I. Systems solely containing a cation-polymerizable monomer, polymer or a mixture thereof as a heat-curable component;
II. Systems containing a cation-polymerizable monomer, polymer or a mixture thereof and a polyol;
III. Systems containing a film-forming, hydroxy group-containing resin and a melamine resin;
IV. Systems capable of curing through a self-condensation reaction of an alkoxysilyl group-containing resin; and
V. Systems capable of curing through a co-condensation reaction of an alkoxysilyl group-containing resin and a hydroxy group-containing resin.
The benzylpyridinium compound of the formula I-a: ##STR2## may be synthesized by reacting a corresponding benzyl halide of the formula II: ##STR3## with a pyridine compound III-a of the formula: ##STR4## and then reacting the resulting benzylpyridium halide with an alkali metal salt of the complex anion MXn-- to metathetically produce the compound I-a.
Similarly, the benzylammonium compound of the formula I-b: ##STR5## may be synthesized by reacting the benzyl halide (II) with a tertiary amine of the formula III-b: ##STR6## and then reacting the resulting benzylammonium halide with an alkali metal salt of the complex anion MXn--.
Among the compounds of formula I-a or I-b, those wherein at least one of R1 -R3 is other than H are preferred. Also preferred are the compounds of the formula I-a wherein R4 is cyano, a halogen or an alkanoyl at the 2 or 4-posion on the pyridine ring.
The compounds of the formula I-a or I-b are thermally cleaved at an elevated temperature to produce a benzyl cation of the formula: ##STR7## which, in turn, initiates a cationic polymerization chain reaction. However, these compounds are substantially inactive at a temperature below their cleaving points. Therefore, they find a number of valuable uses such as a hardener of one-component epoxy resins.
Typical examples of cation-polymerizable monomers are those having a cation-polymerizable functional group such as epoxide, cyclic imine, cyclic ether cyclic ester, and other groups.
For use as a vehicle for coating compositions, adhesives, printing inks and the like, the resin composition may comprise a cation-polymerizable oligomer and/or polymer including the same structure as the above cation-polymerizable monomer in their molecules. The resin composition may be of the solventless type containing the above-mentioned cation-polymerizable monomer and/or a low molecular weight-polyol as a reactive diluent, or it may contain a conventional organic solvent for adjusting its viscosity to a suitable range for application.
Typical examples of cation-polymerizable resins are epoxy resins including bisphenol A--, bisphenol S-- and bisphenol F epoxy resins; novolac type epoxy resins; diglycidyl ethers of glycols such as butanediol, hexanediol and hydrogenated bisphenol A; diglycidyl ethers of polyoxyalkylene glycols such as plyethylene glycol, polypropylene glycol and bisphenol A-alkylene oxide adducts; diglycidyl esters of dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid and adipic acid; and glycidyl ether-esters of hydroxycaboxylic acids such as p- and m-hydroxybenzoic acids.
Also included in examples of preferred cation-polymerizable resins are epoxide group-containing acrylic resins. These acrylic resins are produced by polymerizing a monomer mixture of glycidyl (meth)acrylate with a (meth)acrylic acid ester such as methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate and 2-hydroxyethyl (meth)acrylate optionally containing other comonomers such as styrene or its derivatives, acrylonitrile, vinyl acetate and the like.
Examples of usable polyols include low molecular weight-polyols such as ethylene glycol, propylene glycol, tetrramethylene glycol, diethylene glycol, glycerine, trimethylolpropane and pentaerythritol. It should be noted that these low molecular weight-polyols produce H+ through a chain transfer reaction causing unwanted reactions of cation-polymerizable functional groups. This often results in a cured resin having a low average molecule weight and thus poor mechanical properties. Accordingly, it is more preferable to use an oligomer polyol such as polyether polyols, polycaprolactone polyol, polyester polyols and acryl polyols.
These polyols may be added to the resin composition in such an amount that their hydroxy function is 1 to 100 mole precent relative to the cation-polymerizable functional group. If the amount of polyol is too low, it is difficult to adjust the curing temperature of the resulting composition in a suitable range and the composition is not high solids. Conversely, excessive use of polyols adversely affects the curability of the entire composition.
The composition of this invention contains from 0.01 to 10%, preferably from 0.05 to 5% by weight of the resin solid content of the initiator compound of the formula I-a or I-b. If the amount of the initiator is deficient, the curability of the composition is not satisfactory. Conversely, excessive use of the initiator adversely affects the physical properties of cured composition, such as dark appearance and decreased water resistance.
The composition may contain conventional additives such as pigments, fillers and the like depending upon its intended use.
The resulting composition may be provided as the high solids or solventless type and has an increased storage stability at room temperature although curable at a temperature above the cleaving point of the initiator.
Melamine resin-containing coating compositions or enamels are well-known in the art.
These compositions usually contain a proton-donor such as p-toluenesulfonic acid for catalyzing the cross-linking reaction with the melamine resin. Since the addition of a free acid to the composition tends to cause gelling of the entire composition upon storage, the catalyst is blocked partially or totally in its acid function with an amine which is volatile at the curing temperature of the composition. However, the curability of this type of composition is generally not compatible with the storage stability thereof.
The use of the cationic polymerization initiator of the present invention overcomes this problem. The initiator is substantially inactive until a critical temperature is reached. However, a carbonium cation is liberated from the initiator upon heating to a predetermined temperature and a proton is generated by the reaction of the carbonium cation with water or a hydroxy group-containing compound contained in the composition. This enables for the curability and storage stability of the composition to be compatible.
Various film-forming resins are used in the coating industry in combination with a melamine resin. Examples thereof include polyester resins, polylactone resins, epoxy resins, acrylic resins and the like.
Polyester resins are prepared by the condensation reaction of a polycarboxylic acid or its anhydride with a polyhydric alcohol. Any polyester resin having a hydroxy function at the terminal and/or middle of the polyester chain may be cross-linked with the melamine resin.
Hydroxy terminated polylactone resins may also be cross-linked with the melamine resin.
Epoxy resins having an epoxide function and a hydroxy function at the terminal and the middle of the molecule respectively such as bisphenol epoxy resins and novolac epoxy resins may be used in combination with the melamine resin.
Acrylic resins containing a plurality of hydroxy functions may be prepared by copolymerizing a hydroxy group-containing acrylic monomer such as 2-hydroxyethyl (meth)acrylate with one or more comonomers such as alkyl (meth)acrylates, e.g. methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate and 2-ethylhexyl (meth)acrylate; styrene or its derivatives; (meth)acrylonitrile; vinyl acetate and the like.
Melamine resins are prepared by reacting a triazine compound such as melamine, acetoquanamine or benzoguanamine with formaldehyde, and optionally etherifying the methylol function of the resulting condensate partially or totally with a lower alkanol such as methanol or butanol.
Thermosetting resin compositions comprising a hydroxy group-containing, film-forming resin and a melamine resin are well-known in the coating industry. Except for the use of the above-discussed cationic polymerization initiator, the composition of the present invention may be otherwise identical to these known compositions.
The weight ratio of the hydroxy group-containing, film-forming resin to the melamine resin ranges between 50:50 to 95:5 on the solid content basis.
The composition of this invention contains from 0.01 to 10%, preferably from 0.05 to 5% by weight of the resin solid content of the initiator of the formula I-a or I-b. If the amount of the initiator is deficient, the curability of the composition is not satisfactory. Conversely, excessive use of the intiator adversely affects the physical properties of cured composition such as dark appearance and decreased water resistance.
The composition may contain convenational additives such as pigments, fillers and the like depending upon its intended use.
Japanese Patent Publication No. 33512/88 discloses a curable resin composition containing a vinyl polymer having a plurality of alkoxysilyl group-containing side chains, a polyhydroxy compound and a curing catalyst. It is believed that the composition cures through a self-condensation reaction between two alkoxysilyl groups:
ROSi--+--SiOR+H.sub.2 O→--Si--O--Si--+2ROH
as well as a co-condensation reaction of an alkoxysilyl group and a hydroxy group:
ROSi--+HO--C--→--Si--O--C--+ROH
A variety of catalysts are disclosed as being capable of catalyzing the above reactions. These include amines such as butylamine, dibutylamine, t-butylamine, ethylenediamine and the like; organic metal compounds such as tetraisopropyl titanate, tetrabutyl titanate, tin octate, lead octate, zinc octate, calcium octate, dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate and the like; and acid catalysts such as p-toluenesulfonic acid, trichloroacetic acid and the like. The composition containing these catalysts is curable at room temperature. As is self-explanatory from this fact, the composition cannot be stored for a long period of time while containing the curing catalyst. When long term storage is desired, it is necessary to store the catalyst and the resin component separately and mix the two components immediately prior to use. This is inconvenient in practice and requires to use within a pot life. Other approach includes to reduce the amount of catalyst and blocking the amine or acid catalyst with a suitable acid or amine. Unfortunately they all have been proven unsatisfactory in terms of film properties, storage stabilities and the like.
Similar to the melamine resin-containing composition, the use of the cationic polymerization initiator of the present invention in the above-mentioned system overcomes these problems.
Examples of film-forming resins containing a plurality of alkoxysilyl groups include the following:
A monomer having both an ethylenically unsaturated function and an alkoxysilyl function in the molecule forms a homopolymer or copolymer containing a plurality of alkoxysilyl groups by itself or with acrylic and/or other comonomers.
A first class of such monomers are alkoxysilylalkyl esters of acrylic or methacrylic acid of the formula: ##STR8## wherein R is H or CH3, R' and R" are each alkyl, x is an integer, and n is 0, 1 or 2.
Specific examples of these monomers include
γ-methacryloyloxypropyltrimethoxysilane,
γ-methacryloyloxypropylmethyldimethoxysilane,
γ-methacryloyloxypropyldimethylmethoxysilane,
γ-methacryloyloxypropyltriethoxysilane,
γ-methacryloyloxypropylmethyldiethoxysilane,
γ-methacryloyloxypropyldimethylethoxysilane,
γ-methacryloyloxypropyltripropoxysilane,
γ-methacryloyloxypropylmethyldipropoxysilane,
γ-methacryloyloxypropyldimethylpropoxysilane,
γ-methacryloyloxypropyltributoxysilane,
γ-methacryloyloxypropylmethyldibutoxysilane, and
γ-methacryloyloxypropyldimethylbotoxysilane.
A second class of said monomers are adducts of (meth)acrylic acid with an epoxy group-containing alkoxysilane such as
β-glycidylpropyltrimethoxysilane or
β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.
Another class of alkoxysilyl group-containing monomers are adducts of a hydroxylalkyl (meth)acrylate such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate with an isocyanotoalkylalkoxysilane of the formula:
OCN(CH.sub.2).sub.x Si(R').sub.n (QR").sub.3-n
such as
γ-isocyanatopropyltrimethoxysilane,
γ-isocyanatopropylmethylmethoxysilane,
γ-isocyanatopropyltriethoxysilane or
γ-isocyanatopropylmethyldiethoxysilane.
A further class of alkoxysilyl group-containing monmers are adducts of glycidyl (meth)acrylate with an aminoalkylalkoxysilane such as
γ-aminopropyltrimethoxysilane,
γ-aminopropyltriethoxysilane,
3-(2-aminoethylamino)propylmethyldimethoxysilane,
3-(2-aminoethylamino)propyltrimethoxysilane,
γ-aminopropyldimethylmethoxysilane or
γ-aminopropylmethyldimethoxysilane.
Acrylic and/or other comonomers which may be copolymerized with the alkoxylsilyl group-containing monomer include alkyl (meth)acrylates, (meth)acrylic acid, (meth)acrylonitrile, (meth)arylamide, styrene, vinyl chloride, vinyl acetate and the like.
The above-mentioned aminoalkylalkoxysilanes used for preparing an adduct with glycidyl (meth)acrylate may be reacted with an epoxy resin to produce a modified epoxy resin having a plurality of alkoxysilyl groups.
Polyester resins having a plurality of free carboxyl groups may be modified with the above-mentioned epoxy group-containing alkoxysilane to give silicon-modified polyester resins.
Polyesters having a plurality of hydroxy groups may be reacted with the above-mentioned isocyanatoalkylalkoxysilane to give silicone-modified polyester resins.
Typical examples of hydroxy group-containing resins include polyester resins, polylactone resins, epoxy resins and acrylic resins.
Polyester resins are prepared by the condensation reaction of a polycarboxylic acid or its anhydride with a polyhydric alcohol. Any polyester resin having a hydroxy function at the terminal and/or middle of the polyester chain may be employed.
Hydroxy terminated polylactone resins may also be employed.
Epoxy resins having an epoxide function and a hydroxy function at the terminal and the middle of the molecule respectively, such as bisphenol epoxy resins and novolac epoxy resins may be employed.
Acrylic resins containing a plurality of hydroxy functions may be prepared by copolymerizing a hydroxy group-containing acrylic monomer such as 2-hydroxyethyl (meth)acrylate with one or more comonomers such as alkyl (meth)acrylates, e.g. methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate and 2-ethylhexyl (meth)acrylate, styrene or its derivatives; (meth)acrylonitrile, vinyl acetate and the like.
Systems utilizing the self-condensation reaction of alkoxysilyl groups contain the above-mentioned silicon-containing resin and from 0.01 to 10%, preferably from 0.05 to 5% by weight of the resin solid content of the compound I-b.
Systems utilizing the co-condensation of alkoxysilyl group with hydroxy group contain the above-mentioned silicon-containing resin, an amount of hydroxy group-containing resin at a molar ratio of the hydroxy group per alkoxysilyl group of 0.01 to 10%, preferably from 0.05 to 5% by weight of the resin solid content of the compound I-a or I-b.
If the amount of compound I-a or I-b is deficient, the curability of the composition is not satisfactory. Conversely, excessive addition of the compound I-a or I-b adversely affects the physical properties of cured composition such as dark appearance and decreased water resistance.
The composition may contain conventional additives such as fillers, pigments and the like depending upon its intended use.
The resulting composition has an increased storage stability at room temperature but curable at a temperature above the cleaving point of the compound I-a or I-b. The curing time may vary with the curing temperature but usually within one hour.
The following examples are intended to further illustrate the present invention without limiting thereto. All parts and percents therein are by weight unless otherwise indicated.
4,698 g (0.03 mol) of 4-methoxybenzyl chloride and 10.22 g (0.09 mol) of 2-chloropyridine were reacted in 40 ml of methanol at 40° C. for 3 days. After the reaction, the solvent was evaporate in vacuo and ether-water was added to the residue to extract unreacted reactants in the etherial layer. To the aqueous layer containing the pyridinium chloride was added 7.764 g (0.03 mol) of sodium hexafluoroantimonate. The resulting crystals were suction filtered, washed and dried to give the title compound melting at 122°-124° C.
Analogous to Example I-1, various compounds of the formula I-a listed in the following table were synthesized.
______________________________________
Formula I-a:
##STR9##
No.Example
##STR10## R.sub.4 MXn.sup. -
______________________________________
I-2 4-methylbenzyl 2-Cl SbF.sub.6.sup.-
I-3 2,4-dimethylbenzyl
2-acetyl "
I-4 benzyl 2-Cl PF.sub.6.sup.-
I-5 benzyl " SbF.sub.6.sup.-
I-6 4-methoxybenzyl 4-CN "
I-7 4-methylbenzyl " "
I-8 4-t-butylbenzyl " "
I-9 4-nitrobenzyl " "
I-10 4-chlorobenzyl " "
I-11 2-methylbenzyl 2-CN "
I-12 2-chloro-5-fluoro-
" "
benzyl
I-13 2,3-dimethylbenzyl
" "
I-14 4-methoxybenzyl " "
I-15 2,3-dimethylbenzyl
" "
______________________________________
4,698 g (0.03 mol) of p-methoxybenzyl chloride and 3,638 g (0.03 mol) of N,N-dimethylaniline were reacted in 40 ml of methanol at 40° C. for 3 days. After the reaction, the solvent was evaporated in vacuo and ether/water was added to the residue to extract unreacted reactans in the etherial layer. To the aquous layer containing the ammonium chloride was added 7.77 g (0.03 mol) of sodium hexafluoroantimonate. The resulting crystals were suction filtered, washed and dried to give the titled compound.
NMR: 2.3 ppm (s, 3H, Me), 3.6 ppm (s, 6H, Me), 5.9 ppm (s, 2H, CH2), 7.0 ppm (d, 2H, Ph), 7.3 ppm (d, 2H, Ph), 7.5-7.6 ppm (m, 5H, Ph).
Analogous to Example I-16, various compounds of the formula I-b listed in the following table were sysntheized.
______________________________________
Formula I-b:
##STR11##
No.Example
##STR12##
##STR13## MXn.sup. -
______________________________________
I-17 p-methylbenzyl N,N-dimethyl-
SbF.sub.6.sup.-
anilinium
I-18 p-t-butylbenzyl N,N-dimethyl-
"
anilinium
I-19 p-chlorobenzyl N,N-dimethyl-
"
anilinium
I-20 p-nitrobenzyl N,N-dimethyl-
"
anilinium
I-21 p-chlorobenzyl N,N-dimethyl-
PF.sub.6.sup.-
anilinium
I-22 p-methylbenzyl N,N-dimethyl-
"
anilinium
I-23 " N,N-dimethyl-
BF.sub.4.sup.-
N-(m-tolyl)
ammonium
I-24 benzyl N,N-dimethyl-
SbF.sub.6.sup.-
anilinium
I-25 benzyl N,N-dimethyl-
"
N-(p-tolyl)
ammonium
I-26 O-methylbenzyl N,N-dimethyl-
"
anilinium
I-27 O-chlorobenzyl N,N-dimethyl-
"
anilinium
I-28 2,3-dimethylbenzyl
N,N-dimethyl-
"
anilinium
I-29 p-methoxybenzyl N,N-dimethyl-
"
anilinium
I-30 p-methylbenzyl N,N-dimethyl-
"
N-(p-tolyl)
ammonium
I-31 " N,N-dimethyl-
PF.sub.6.sup.-
N-(p-tolyl)
ammonium
I-32 2-chloro-5- N,N-dimethyl-
fluorobenzyl anilinium SbF.sub.6.sup.-
I-33 O-methylbenzyl N,N-dimethyl-
SbF.sub.6.sup.-
anilinium
______________________________________
A reaction vessel provided with a heater, stirrer, reflux condenser, water separator, fractional distillation column and thermometer was charged with 36 parts of hexahydrophthalic acid, 42 parts of trimethylolpropane, 50 parts of neopentyl glycol and 56 parts of 1,6-hexanediol. The mixture was heated to 210° C. with stirring. Then the mixture was heated to 230° C. at a constant rate over 2 hours while distilling out water formed as a by-product by the condensation reaction. The reaction was continued at 230° C. until an acid number of 1.0 was reached and stopped by cooling. After the addition of 153 parts of isophthalic acid, the reaction mixture was heated again to 190° C. and thereafter from 190° C. to 210° C. at a constant rate over 3 hours while distilling out formed water. When this temperature was reached, 3 parts of xylene was added and the reaction was continued until an acid number of 5.0 was reached. After cooling, the reaction mixture was diluted with 190 parts of xylene whereupon Polyester solution A was obtained.
Using a conventional technique, Acrylic resin solution A having a molecular weight of 3,500, a solution viscosity of M-N and a nonvolatile content of 60.5% was produced by solution polymerizing the following mixture at 120° C.
______________________________________
Formulation Parts
______________________________________
Methyl methacrylate
28.11
Styrene 25.00
Glycidyl methacrylate
30.00
n-Butyl acrylate 2.59
Isobutyl methacrylate
1.88
Azobisisobutyronitrile
5.00
______________________________________
Analogous to Example II-1, Acrylic resin solution B having a molecular weight of 4,200, a solution viscosity of U-V and a nonvolatile content of 60.2% was produced from the following mixture.
______________________________________
Formulation Parts
______________________________________
Methyl methacrylate
23.11
Styrene 30.00
Glycidyl methacrylate
30.00
n-Butylacrylate 1.88
Isobutyl methacrylate
12.42
Azobisisobutyronitrile
5.00
______________________________________
Analogous to Example II-1, the following mixture was solution polymerized at 120° C.
______________________________________
Formulation Parts
______________________________________
Methyl methacrylate 23.1
Styrene 30.00
n-Butyl acrylate 2.59
Isobutyl methacrylate
1.88
2-Hydroxyethyl methacrylate
12.42
Azobisisobutyronitrile
5.00
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After the polymerization, 10.2 parts of p-vinylbenzoic acid was added to 60 parts (as solid content) of the resulting polymer and the mixture reacted at 200° C. until an acid number of 0.9 was reached. Acrylic resin solution C having a molecular weight of 4,300, a solution viscosity of Q-R and a nonvolatile content of 64.7% was obtained.
A reaction vessel provided with a stirrer, thermometer, reflux condenser, nitrogen gas-introducing tube and dripping funnel was charged with 90 parts of SOLVESSO 100 and heated to 160° C. while introducing nitrogen gas. To the vessel was added dropwise the following monomer mixture at a constant rate:
______________________________________
2-Hydroxyethyl methacrylate
23.20 parts
Methyl methacrylate 38.85 parts
n-Butyl acrylate 35.65 parts
Methacrylic acid 2.30 parts
t-Butylperoxy-2-ethylhexanoate
10.00 parts
______________________________________
One hour after the addition, a mixture of 10 parts of xylene and 1 part of t-butylperoxy-2-ethylhexanoate was added dropwise at a constant rate over 30 minutes. The reaction was allowed to proceed to completion for 2 hours and stopped by cooling to give Acrylic Resin D.
Analogous to Example II-5, Acrylic Resin E was prepared from the following monomer mixture:
______________________________________
IsobutyI methacrylate
1.88 parts
n-Butyl acrylate 2.59 parts
Methyl methacrylate 28.11 parts
Styrene 25.00 parts
Glycidyl methacrylate
30.00 parts
t-Butylperoxy-2-ethylhexanoate
5.00 parts
______________________________________
Analogous to Example II-5, Acrylic Resin F was prepared from the following monomer mixture:
______________________________________
2-Hydroxyethyl methacrylate
12.42 parts
n-Butyl acrylate 2.59 parts
Methyl methacrylate 23.11 parts
Styrene 30.00 parts
Glycidyl methacrylate
30.00 parts
t-Butylperoxy-2-ethylhexanoate
5.00 parts
______________________________________
A reaction vessed used in Example II-5 was charged with 45 parts of xylene and heated to 130° C. while introducing nitrogen gas. To the vessel was added dropwise a mixture of 50 parts of γ-methacryloyloxypropyltrimethoxysilane and 4 parts of t-butylperoxy-2-ethyl-hexanoate at a constant rate over 3 hours.
30 minutes after the addition, the mixture was cooled to 90° C., and a mixture of 1 part of butylperoxy-2-ethylhexanoate and 5 parts of xylene was added thereto. The reaction was allowed to proceed to completion for additional 2 hours and stopped by cooling to give Silicon Resin A.
Analogous to Example II-8, a mixture of 50 parts of γ-methacryloyloxypropylmethyldimethoxysilane and 4 parts of t-butylperoxy-2-ethylhexanoate was polymerized to give Silicon Resin B.
Analogous to Example II-8, a mixture of 50 parts of γ-methacryloyloxypropyldimethylmethoxysilane and 4 parts of t-butylperoxy-2-ethylhexanoate was polymerized to give Silicon Resin C.
Analogous to Example II-8, a mixture of 50 parts of γ-methacryloyloxypropyltriethoxysilane and 4 parts of t-butylperoxy-2-ethylhexanoate was polymerized to give Silicon Resin D.
Analogous to Example II-8, a mixture of 25 parts of γ-methacryloyloxypropyltriethoxysilane, 25 parts of methyl methacrylate and 4 parts of t-butylperoxy-2-ethylhexanoate was polymerized to give Silicon Resin E.
A reaction vessel provided with a stirrer, thermometer and reflux condenser was charged with 100 parts of Polyester Resin A obtained in Example I-1 and heated to 100° C. After the addition of 0.2 parts of dibutyltin dilaurate, 10 parts of KBK-9007 (chemically γ-isocyanatopropyltrimethoxysilane sold by Shin-Etsu Chemical Co., Ltd.) were added dropwise at a constant rate over 30 minutes and the reaction allowed to proceed to completion for additional 1 hour. After cooling, Silicon Resin F was obtained. The adsorption of NCO group at 1720 cm-1 disappeared completely in the IR spectrometry of the resin.
A reaction vessel provided with a stirrer, thermometer and reflux condenser was charged with 100 parts of bisphenol A diglycidyl ether and heated to 150° C. Then 100 parts of γ-aminopropyltrimethoxysilane were added dropwise at a constant rate over 1 hour and allowed to react for additional 1 hour. After cooling, Silicon Resin G was obtained.
0.5 parts of an initiator listed below was uniformly mixed with 100 parts of Acrylic Resin A, B or EPITOTO YD-014 (epoxy resin sold by Toto Kasei Co., Ltd.). The mixture was cast on a tinplate and baked at a temperature from 90° C. to 160° C. for 30 minutes. The curing state of each sample was observed and the results are shown in Table III-1.
A: 1-(4-methoxybenzyl)-4-cyanopyridinium hexafluoroantimonate
B: 1-(4-methylbenzyl)-4-cyanopyridinium hexafluoroantimonate
C: 1-(4-t-butylbenzyl)-4-cyanopyridinium hexafluoroantimonate
D: 1-(4-nitrobenzyl)-4-cyanopyridinium hexafluoroantimonate
E: 1-(4-chlorobenzyl)-4-cyanopyridinium hexafluoroantimonate
F: 1-(2-methylbenzyl)-2-cyanopyridinium hexafluoroantimonate
G: 1-(2-chloro-5-fluorobenzyl)-2-cyanopyridinium hexafluoroantimonate
H: 1-(2,3-dimethylbenzyl)-2-cyanopyridinium hexafluoroantimonate
I: 1-(4-methoxybenzyl)-2-cyanopyridinium hexafluoroantimonate
J: 1-(2,3-dimethylbenzyl)-2-methylpyridinium hexafluoroantimonate
K: Boron trifluoride diethyl ether complex (for comparison)
L: 1-(p-t-butylbenzyl)tetrahydrothiophenium hexafluoroantimonate (for comparison)
TABLE III-1
__________________________________________________________________________
Curing State
Temperature, °C.
Run No.
Polymer
Initiator
90
100
110
120
130
140
150
160
Malodor
__________________________________________________________________________
1 A A x x Δ
◯
◯
◯
◯
◯
No
2 " B x x x x Δ
◯
◯
◯
"
3 " C x x x Δ
◯
◯
◯
◯
"
4 " D x x x x Δ
◯
◯
◯
"
5 " E x x x x x ◯
◯
◯
"
6 B B x x Δ
◯
◯
◯
◯
◯
"
7 YD-014
B x x x Δ
◯
◯
◯
◯
"
8 " A x Δ
Δ
Δ
◯
◯
◯
◯
"
9 " E x x x Δ
Δ
◯
◯
◯
"
10 " C x x Δ
◯
◯
◯
◯
◯
"
11 A K Gelling at R.T. immediately
"
after mixing.
12 A L x x x x Δ
◯
◯
◯
Yes
__________________________________________________________________________
◯: Fully cured;
Δ: Partially cured;
x: Tacky
0.5 parts of the initiator was uniformly mixted with Acrylic Resin C. The mixture was cast on a tinplate and baked at a temperature from 90° C. to 160° C. for 30 minutes. The curing state of each sample was observed and results are shown in Table III-2.
TABLE III-2
__________________________________________________________________________
Curing State
Temperature, °C.
Run No.
Polymer
Initiator
90
100
110
120
130
140
150
160
Malodor
__________________________________________________________________________
1 C A x x x x Δ
◯
◯
◯
No
2 " B x x x x x x Δ
◯
"
3 " C x x x x x Δ
◯
◯
"
4 " D x x x x x Δ
◯
◯
"
5 " F x x x Δ
◯
◯
◯
◯
"
6 " G x x x x x x Δ
◯
"
7 " K Gelling at R.T. immediately
"
after mixing.
8 " L x x x x x x Δ
◯
Yes
__________________________________________________________________________
◯: Fully cured;
Δ: Partially cured;
x: Tacky
0.5 parts of the initiator was uniformly mixted with 100 parts of ERL-4206(alicyclic epoxy resin sold by UCC). The mixture was cast on a tinplate and baked at a temperature from 90° C. to 160° C. The cured state of each sample was observed and the results are shown in Table III-3.
TABLE III-3
__________________________________________________________________________
Curing State
Temperature, °C.
Run No.
Polymer
Initiator
90
100
110
120
130
140
150
160
Malodor
__________________________________________________________________________
1 ERL-4206
H x Δ
◯
◯
◯
◯
◯
◯
No
2 " I x Δ
◯
◯
◯
◯
◯
◯
"
3 " J x Δ
◯
◯
◯
◯
◯
◯
"
4 " K Gelling at R.T. immediately
"
after mixing.
5 " L x x x ◯
◯
◯
◯
◯
Yes
__________________________________________________________________________
◯: Fully cured;
Δ: Partially cured;
x: Tacky
0.5 parts of N-(2,3-dimethylbenzyl)-N,N-dimethylanilinium hexafluoroantimonate was uniformly mixted with Acrylic Resin F and 10 parts of ERL-4206. The mixture was cast on a tinplate and baked at 120° C. The curability of the composition as well as its storage stability was tested and the results are shown in Table III-4.
Analogous to Example III-4, the following compositions were tested for the curability and storate stability. The results are also shown in Table III-4.
Initiator of the formula:
______________________________________
##STR14##
(parts
Exam- Initiator solid
ple A (parts) Resin content)
______________________________________
III-5 p-chlorobenzyl
0.5 Acrylic F 70
ERL-4206 30
III-6 benzyl 0.1 Acrylic E 90
III-7 p-chlorobenzyl
2.0 Acrylic E 90
III-8 p-methylbenzyl
0.07 Acrylic E 90
III-9 O-methylbenzyl
0.5 Acrylic E 90
III-10
benzyl 1.0 Acrylic F 90
III-11
p-chlorobenzyl
0.05 Acrylic F 90
III-12
p-methylbenzyl
4.0 Acrylic F 90
III-13
O-methylbenzyl
0.3 Acrylic F 90
III-14
2,3-dimethylbenzyl
0.5 ERL-4206 100
III-15
p-methylbenzyl
0.06 EPIKOTE1001
100
______________________________________
TABLE III-4
__________________________________________________________________________
Example
III-4 III-5
III-6
III-7
III-8
III-9
III-10
III-11
III-12
III-13
III-14
III-15
__________________________________________________________________________
Curability.sup.1
⊚
◯
◯
◯
◯
◯
⊚
⊚
⊚
⊚
⊚
◯
Storage
◯
⊚
⊚
⊚
◯
⊚
◯
⊚
⊚
◯
◯
⊚
Stability.sup.2
__________________________________________________________________________
.sup.1 Appearance of cured film after the MEK rubbing test (100
reciprocations).
⊚: No change;
◯: Slightly dissolved;
Δ: Whitening;
x: Dissolved
.sup.2 Increase in viscosity after storing in a closed system at
40° C. for 2 weeks.
⊚: No increase;
◯: Slightly increased;
Δ: Increased;
x: Gelling
100 parts of Acrylic Resin A were thoroughly mixed with 0.5 parts of 1-(p-t-butylbenzyl)-4-cyanopyridinium hexafluoroantimonate and 2.95 parts of PLACCEL 308 (trifuctional polycaprolactone polyol having a molecular weight of 860 sold by Daicel Chemical Industries, Ltd.). The mixture was cast on a tinplate and baked at 130° C. or 150° C. for 30 minutes.
The curability determined by the finger test and the initial viscosity of the mixture are shown in Table IV-1.
Analogous to Example IV-1, the following compositions were tested for the curability and initial viscosity. The results are also shown in Table IV-1.
Initiator of the formula:
______________________________________
##STR15##
Ex-
am- Initiator
ple A R.sub.4 (parts)
Resin (parts)
______________________________________
IV-2 p-t-butylbenzyl,
4-CN, 0.5 Acrylic A
100
Placcel 308
5.9
IV-3 p-t-butylbenzyl,
4-CN, 0.5 Acrylic A
100
Placcel 308
11.8
IV-4 p-t-butylbenzyl,
4-CN, 0.5 Acrylic A
100
Placcel 308
29.5
IV-5 2,4-dichlorobenzyl,
4-CN, 0.5 Acrylic A
100
Polyether-
2.95
polyol 1)
IV-6 2,4-dichlorobenzyl,
4-CN, 0.5 Acrylic A
100
Polyether-
5.9
polyol
IV-7 2,4-dichlorobenzyl,
4-CN, 0.5 Acrylic A
100
Polyether-
11.8
polyol
IV-8 2,4-dichlorobenzyl,
4-CN, 0.5 Acrylic A
100
Polyether-
29.5
polyol
______________________________________
1) Trifunctional polyetherpolyol, M.W. = 800
TABLE IV-1
______________________________________
Example
Temp. IV-1 IV-2 IV-3 IV-4 IV-5 IV-6 IV-7 IV-8
______________________________________
130° C.
Δ
Δ-◯
◯
◯
Δ
Δ-◯
◯
◯
150° C.
Δ
◯
◯
◯
Δ
◯
◯
◯
Viscosity
L-M J G-H F K I G D
______________________________________
Curability:
◯: Fully cured;
Δ: Fairly cured
x: Not cured
Viscosity: Measured by Gardener's bubble viscometer.
Analogous to Example IV-1, the following compositions were tested for the curability, storage stability and initial viscosity. The results are shown in Table IV-2.
TABLE IV-2
______________________________________
Example
IV-9 IV-10 IV-11
______________________________________
Initiator (1)
A 0.5 B 0.5 C 0.5
(parts)
Resin Acrylic E 100
Acrylic E 100
Acrylic E 100
(parts) Placcel 308
1,6-hexane- Polyether-5
2.95 diol polyol (2)
Curability (3)
⊚
⊚
◯
Storage ◯
◯
⊚
stability (4)
Initial L-M J K
viscosity (5)
______________________________________
(1) A = N(p-t-butylbenzyl)-N,N-dimethylanilinium hexafluoroantimonate
B = (pmethylbenzyl)-N,N-dimethylanilinium hexafluoroantimonate
C = Nbenzyl-N,N-dimethylanilinium hexafluoroantimonate
(2) Trifunctional polyetherpolyol, M.W. = 800
(3) Film appearance after the MEK rubbing test (100 reciprocations).
⊚: No change;
◯: Slightly dissolved;
Δ: Whitening;
x: Dissolved
(4) Viscosity increase after storing in a closed system at 40° C.
for 2 weeks.
⊚: No increase;
◯: Slightly increased;
Δ: Increased;
x: Gelling
(5) Measured by Gardener's bubble viscometer.
Part V. Systems Containing Melamine Resin
70 parts of PLACCEL 308, 30 parts of CYMEL 303 (melamine resin sold by Mitsui Toatsu Chemicals, Inc.) and 2 parts of 1-(4-methylbenzyl)-4-cyanopyridinium hexafluoroantimonate were thoroughly mixted. The mixture was cast on a tinplate and baked at 140° C. The curability and storage stability of the mixture are shown in Table V-1.
Analogous to Example V-1, the following compositions were tested for the curability and storate stability. The results are shown in Table V-1.
Initiater of the formula:
______________________________________
##STR16##
Initiator
Example A, R.sub.4, MXn.sup.-,
parts Resin, parts
______________________________________
V-2 4-chlorobenzyl,
2 Placcel 308
70
2-CH.sub.3, SbF.sub.6.sup.-,
Cymel 303 30
V-3 2,4-dichlorobenzyl,
2 Placcel 308
50
2-CH.sub.3, PF.sub.6.sup.-,
Cymel 303 50
V-4 2-methylbenzyl,
0.1 Polyester A
90
2-CH.sub.3, PF.sub.6.sup.-,
(solid content)
Cymel 303 10
V-5 2,4-dimethylbenzyl,
2 Polyester A
60
2-Cl, PF.sub.4.sup.-, (solid content)
Yuban 20SE 1)
40
(solid content)
V-6 4-methoxybenzyl,
7 Polyester A
70
3-Cl, BF.sub.4.sup.-, (solid content)
Yuban 20SE
30
(solid content)
V-7 benzyl, 2-CH.sub.3, SbF.sub.6.sup.-
2 Acrylic D 90
(solid content)
Cymel 303 10
V-8 2-chlorobenzyl,
2 Acrylic D 60
2-CN, PF.sub.6.sup.-, (solid content)
Yuban 20S 40
(solid content)
V-9 4-methoxybenzyl,
0.5 Acrylic D 70
4-Cl, SbF.sub.6.sup.-, (solid content)
Yuban 20S 30
(solid content)
V-10 p-toluenesulfonic acid/
2 Placcel 308
70
triethylamine salt Cymel 303 30
(for comparison)
V-11 p-dodecylbenzene-
2 Plyester A
90
sulfonic acid/ (solid content)
pyridine salt Cynel 303 10
(for comparison)
V-12 p-toluenesulfonic acid/
2 Acrylic D 60
pyridine salt (solid content)
(for comparison) Yuban 20S 40
(solid content)
______________________________________
1) Melamine resin sold by Mitsui Toatsu Chemicals, Inc.
TABLE V-1
__________________________________________________________________________
Example
V-1 V-2
V-3
V-4
V-5
V-6
V-7
V-8
V-9
V-10
V-11
V-12
__________________________________________________________________________
Curability.sup.1
⊚
◯
◯
◯
⊚
◯
⊚
◯
◯
◯
⊚
⊚
Storage
◯
⊚
⊚
⊚
◯
⊚
⊚
⊚
◯
Δ
x x
Stability.sup.2
__________________________________________________________________________
.sup.1 Film appearance after the MEK rubbing test (100 reciprocations).
⊚: No change;
◯: Slightly changed;
Δ: Whitening;
x: Dissolved
.sup.2 Viscosity increase after storing in a closed system at 40°
C. for 2 weeks.
⊚: No increase;
◯: Slightly increased;
Δ: Increased;
x: Gelling
Analogous to Example V-1, the following compositions were tested for the curability and storage stability. The results are shown in Table V-2.
Initiator of the formula:
______________________________________
##STR17##
Initiator
Example
A, MXn, parts Resin, parts
______________________________________
V-13 4-methylbenzyl, SbF.sub.6.sup.-,
2 Placcel 308
70
Cymel 303 30
V-14 4-chlorobenzyl, SbF.sub.6.sup.-,
2 Placcel 308
70
Cymel 303 30
V-15 2,4-dichlorobenzyl, PF.sub.6.sup.-
1 Placcel 308
50
Cymel 303 50
V-16 2-methylbenzyl, PF.sub.6.sup.-
0.1 Polyester A
90
(solid content)
Cymel 303 10
V-17 2,4-dimethylbenzyl, BF.sub.4.sup.-
2 Polyester A
60
(solid content)
Yuban 20S 40
(solid content)
V-18 4-methoxybenzyl, BF.sub.4.sup.-,
7 Polyester A
70
(solid content)
Yuban 20S 30
(solid content)
V-19 benzyl, SbF.sub.6.sup.-,
2 Acrylic D 90
(solid content)
Cymel 303 10
V-20 2-chlorobenzyl, PF.sub.6.sup.-,
2 Acrylic D 60
(solid content)
Yuban 20S 40
(solid content)
V-21 4-methoxybenzyl, SbF.sub.6.sup.-,
0.5 Acrylic D 70
(solid content)
Yuban 20S 30
(solid content)
______________________________________
TABLE V-2
______________________________________
Example
V-13 V-14 V-15 V-16 V-17 V-18 V-19 V-20 V-21
______________________________________
Cura- ⊚
◯
◯
◯
⊚
◯
⊚
◯
◯
bility.sup.1
Stor- ◯
⊚
⊚
⊚
◯
⊚
⊚
⊚
◯
age
Stabil-
ity.sup.2
______________________________________
.sup.1 Film appearance after the MEK rubbing test (100 reciprocations).
⊚: No change;
◯: Slightly changed;
Δ: Whitening;
x: Dissolved
.sup.2 Viscosity increase after storing in a closed system at 40°
C. for 2 weeks.
⊚No change;
◯: Slightly increased;
Δ: Increased;
x: Gelling
100 parts of Acrylic Resin D, 30.7 parts of Silicon Resin A, 5 parts of methanol and 2.62 parts of 1-benzyl-4-cyanopyridinium hexafluoroantimonate were thoroughly mixed. The mixture was cast on a steel plate, allowed to set for 2 hours and baked at 140° C. for 30 minutes. The curability and storage stability of the mixture are showen in Table VI-1.
Analogous to Example VI-1, the following compositions were tested for the curability and storage stability. The results are shown in Table VI-1.
Initiator of the formula:
______________________________________
##STR18##
Initiator
Example
A, R.sub.4, MXn, parts
Resin, parts
______________________________________
VI-2 2-chlorobenzyl, 4-CN,
2.58 Acrylic D
100
SbF.sub.6.sup.-, Silicon B
28.5
Methanol 5
VI-3 2,4-dichlorobenzyl,
2.54 Acrylic D
100
4-CN, SbF.sub.6.sup.-, Silicon C
26.9
Methanol 5
VI-4 2-methylbenzyl, 2-CN,
2.72 Acrylic D
100
SbF.sub.6.sup.-, Silicon D
36.2
Methanol 5
VI-5 4-nitrobenzyl, 2-CH.sub.3,
2.87 Acrylic D
100
SbF.sub.6.sup.-, Silicon E
43.4
Methanol 5
VI-6 2-methylbenzyl, 4-F,
2.87 Polyester A
100
PF.sub.6.sup.-, Silicon F
30
Methanol 5
VI-7 4-methoxybenzyl, H,
2.87 Polyester A
100
PF.sub.6.sup.-, Silicon G
18
Methanol 5
VI-8 2-chlorobenzyl, 4-CN,
2 Silicon A
100
SbF.sub.6.sup.-, Methanol 5
VI-9 2-chlorobenzyl, 4-CN,
2 Silicon C
100
SbF.sub.6.sup.-, Methanol 5
VI-10 2-chlorobenzyl, 4-CN,
2 Silicon F
100
SbF.sub.6.sup.-, Methanol 5
VI-11 None (for comparison) Acrylic A
100
Silicon A
30.9
Methanol 5
VI-12 dodecylbenzenesulfonic
2.62 Acrylic A
100
acid (for comparison) Silicon A
30.9
Methanol 5
VI-13 None (for comparison) Silicon A
100
Methanol 5
VI-14 dodecylbenzenesulfonic
2 Silicon A
100
acid (for comparison) Methanol 5
______________________________________
TABLE VI-1
______________________________________
Example
VI-1 VI-2 VI-3 VI-4 VI-5 VI-6 VI-7
______________________________________
Cura- ⊚
⊚
⊚
⊚
⊚
⊚
⊚
bility.sup.1
Storage
◯
◯
◯
◯
◯
◯
◯
stability.sup.2
______________________________________
Example
VI-8 VI-9 VI-10 VI-11 VI-12 VI-13 VI-14
______________________________________
Cura- ⊚
⊚
⊚
x ⊚
x ⊚
bility.sup.1
Storage
◯
◯
◯
◯
x ◯
x
stability.sup.2
______________________________________
.sup.1 Film appearance after the MEK rubbing test (100 reciprocations).
⊚: No change;
◯: Slightly changed;
Δ: Whitening;
x: Dissolved
.sup.2 Viscosity increase after storing in a closed system at 40°
C. for 2 weeks.
⊚: No change;
◯: Slightly increased;
Δ: increased;
x: Gelling;
Analogous to Example VI-1, the following compositions were tested for the curability and storage stability. The results are shown in Table VI-2.
Initiator of the formula:
______________________________________
##STR19##
Initiator
Example
A, MXn, parts Resin, parts
______________________________________
VI-15 benzyl, Sb.sub.6.sup.-
2.62 Acrylic A
100
Silicon A
30.7
Methanol 5
VI-16 2-chlorobenzyl, SbF.sub.6.sup.-
2.58 Acrylic A
100
Silicon B
28.9
Methanol 5
VI-17 2,4-dichlorobenzyl,
2.54 Acrylic A
100
SbF.sub.6.sup.- Silicon C
26.9
Methanol 5
VI-18 2-methylbenzyl, SbF.sub.6.sup.-
2.72 Acrylic A
100
Silicon D
36.2
Methanol 5
VI-19 4-nitrobenzyl, SbF.sub.6.sup.-
2.87 Acrylic A
100
Silicon E
43.4
Methanol 5
VI-20 2-methylbenzyl, PF.sub.6.sup.-
2.87 Acrylic A
100
Silicon F
30
Methanol 5
VI-21 4-methoxybenzyl, PF.sub.6.sup.-
2.87 Polyester A
100
Silicon G
18
Methanol 5
VI-22 N-benzyl-N-(2-tolyl)-
2.58 Silicon B
100
N,N-dimethylammonium Methanol 5
hexafluoroantimonate
______________________________________
TABLE VI-2
______________________________________
Example
VI-15 VI-16 VI-17 VI-18
______________________________________
Curability.sup.1)
⊚
⊚
⊚
⊚
Storage ◯
◯
◯
◯
stability.sup.2)
______________________________________
Example
VI-19 VI-20 VI-21 VI-22
______________________________________
Curability.sup.1)
⊚
⊚
⊚
⊚
Storage ◯
◯
◯
◯
stability.sup.2)
______________________________________
.sup.1) Film appearance after the MEK rubbing test (100 reciprocations).
⊚: No change; ◯: Slightly changed;
Δ: Whitening; x: Dissolved
.sup.2) Viscosity increase after storing in a closed system at 40°
C. for 2 weeks.
⊚: No change; ◯: Slightly increased;
Δ: increased; x: Gelling;
Claims (3)
1. In a heat curable resinous composition comprising a polymerization initiator and a resin capable of curing upon heating in the presence thereof, the improvement wherein the polymerization initiator is 0.01 to 10% by weight of the solid content of said resin of a compound of the formula: ##STR20## wherein R1, R2, R3 and R4 are each H, OH, halogen, an alkyl, an alkoxy, nitro, amino, an alkylamino, an alkanoyl, cyano, an alkoxycarbonyl or carbamoyl;
R5, R6 and R7 are each an alkyl, an alkenyl or phenyl which may be substituted with nitro, cyano, amino, halogen, an alkyl, an alkoxy or a dialkylamino, at least one of R5, R6 and R7 being phenyl or the substituted phenyl;
M is As, Sb, B or P;
X is halogen; and
m equals the valency of the element M plus one.
2. The resinous composition according to claim 1, wherein said resin is a monomer or polymer having a cation polymerizable function, or a mixture thereof.
3. The resinous composition according to claim 2, wherein said cation polymerizable function is epoxide, cyclic imine, cyclic ether or vinyl.
Applications Claiming Priority (12)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63-131171 | 1988-05-27 | ||
| JP13117188A JPH01299803A (en) | 1988-05-27 | 1988-05-27 | Thermosetting resin composition |
| JP13117088A JPH082876B2 (en) | 1988-05-27 | 1988-05-27 | New benzylpyridinium salt |
| JP63-131170 | 1988-05-27 | ||
| JP33380288A JPH02178319A (en) | 1988-12-28 | 1988-12-28 | Thermosetting composition |
| JP63-333802 | 1988-12-28 | ||
| JP5267389A JPH0778159B2 (en) | 1989-03-03 | 1989-03-03 | Thermosetting resin composition |
| JP1-526731 | 1989-03-03 | ||
| JP1079468A JPH075524B2 (en) | 1989-03-29 | 1989-03-29 | New benzyl ammonium salt |
| JP1-794681 | 1989-03-29 | ||
| JP1106738A JPH02283777A (en) | 1989-04-25 | 1989-04-25 | Thermosetting resin composition |
| JP1-106738 | 1989-04-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US5070161A true US5070161A (en) | 1991-12-03 |
Family
ID=27550500
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/356,903 Expired - Lifetime US5070161A (en) | 1988-05-27 | 1989-05-25 | Heat-latent, cationic polymerization initiator and resin compositions containing same |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5070161A (en) |
| EP (1) | EP0343690B1 (en) |
| CA (1) | CA1329607C (en) |
| DE (1) | DE68921243T2 (en) |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5231186A (en) * | 1991-03-22 | 1993-07-27 | Nippon Paint Co., Ltd. | Quaternary ammonium salts |
| US5326827A (en) * | 1990-11-14 | 1994-07-05 | Nippon Paint Co., Ltd. | Heat-curable resin composition containing acrylic polymer having alicyclic epoxide functions |
| US6019507A (en) * | 1992-11-25 | 2000-02-01 | Terumo Cardiovascular Systems Corporation | Method of making temperature sensor for medical application |
| US6162950A (en) * | 1999-12-03 | 2000-12-19 | Albemarle Corporation | Preparation of alkali metal tetrakis(F aryl)borates |
| US6169208B1 (en) | 1999-12-03 | 2001-01-02 | Albemarle Corporation | Process for producing a magnesium di[tetrakis(Faryl)borate] and products therefrom |
| WO2002006354A1 (en) * | 2000-07-13 | 2002-01-24 | Mcneese State University | Use of deaminatively-generated carbocation as polymerization initiators |
| US6376638B1 (en) | 1998-10-28 | 2002-04-23 | Korea Research Institute Of Chemical Technology | Latent curing agent for epoxy resin initiated by heat and UV-light and epoxy resin composition containing the same and cured epoxy products |
| US6709741B1 (en) * | 2001-09-07 | 2004-03-23 | Taiflex Scientific Co., Ltd. | FPC adhesive of epoxy resin, onium hexafluoroantimonate, nitrile rubber and filler |
| US6773474B2 (en) | 2002-04-19 | 2004-08-10 | 3M Innovative Properties Company | Coated abrasive article |
| US20040230075A1 (en) * | 2002-10-03 | 2004-11-18 | Lee John Y. | Process for producing tetrakis(Faryl)borate salts |
| US20050215713A1 (en) * | 2004-03-26 | 2005-09-29 | Hessell Edward T | Method of producing a crosslinked coating in the manufacture of integrated circuits |
| US6977274B2 (en) * | 1999-01-30 | 2005-12-20 | Korea Research Institute Of Chemical Technology | Epoxy resin curing system containing latent catalytic curing agent causing the expansion of volume |
| US20060110600A1 (en) * | 2004-11-19 | 2006-05-25 | 3M Innovative Properties Company | Anisotropic conductive adhesive composition |
| US20070116961A1 (en) * | 2005-11-23 | 2007-05-24 | 3M Innovative Properties Company | Anisotropic conductive adhesive compositions |
| US20080012124A1 (en) * | 2006-05-16 | 2008-01-17 | Stapleton Russell A | Curable protectant for electronic assemblies |
| US20090311502A1 (en) * | 2006-07-24 | 2009-12-17 | Mccutcheon Jeffrey W | Electrically conductive pressure sensitive adhesives |
| US8846160B2 (en) | 2008-12-05 | 2014-09-30 | 3M Innovative Properties Company | Three-dimensional articles using nonlinear thermal polymerization |
| CN108957952A (en) * | 2017-05-17 | 2018-12-07 | 东京应化工业株式会社 | Solidification compound, cured film, the manufacturing method of display panel and solidfied material |
| WO2023180035A1 (en) | 2022-03-22 | 2023-09-28 | Delo Industrie Klebstoffe Gmbh & Co. Kgaa | Low-temperature-curing compounds based on glycidyl ethers |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU627316B2 (en) * | 1989-06-05 | 1992-08-20 | Nippon Paint Co., Ltd. | Antimony, arsenic, boron and phosphorous halide salts of quaternary ammonium compounds |
| EP0441232A3 (en) * | 1990-02-09 | 1992-10-14 | Basf Aktiengesellschaft | Cationic photopolymerisation process |
| FR2727416A1 (en) * | 1994-11-24 | 1996-05-31 | Rhone Poulenc Chimie | Heat activated cationic polymerisation and crosslinking initiators |
| CN104031243A (en) * | 2014-06-24 | 2014-09-10 | 上海大学 | Quaternary ammonium salt epoxy resin curing accelerator and preparation method thereof |
| DE102016111590A1 (en) | 2016-06-24 | 2017-12-28 | Delo Industrie Klebstoffe Gmbh & Co. Kgaa | One-component composition based on alkoxysilanes and method for joining or casting components using the composition |
| DE102017126215A1 (en) | 2017-11-09 | 2019-05-09 | Delo Industrie Klebstoffe Gmbh & Co. Kgaa | A process for producing opaque coatings, bonds and potting and curable composition for use in the process |
| DE102019129517A1 (en) | 2019-10-31 | 2021-05-06 | Delo Industrie Klebstoffe Gmbh & Co. Kgaa | Cationically moisture-induced hardenable mass, use of the mass and methods for joining, potting and coating substrates |
| DE102020118813A1 (en) | 2020-07-16 | 2022-01-20 | Delo Industrie Klebstoffe Gmbh & Co. Kgaa | Repositionable compositions based on polyacetals |
| DE102021110210A1 (en) | 2021-04-22 | 2022-10-27 | Delo Industrie Klebstoffe Gmbh & Co. Kgaa | Method of manufacturing an optical module and optical module |
| DE102021122835A1 (en) | 2021-09-03 | 2023-03-09 | Delo Industrie Klebstoffe Gmbh & Co. Kgaa | Heat-curing compound based on (meth)acrylates and peroxodicarbonates |
| DE102022102650A1 (en) | 2022-02-04 | 2023-08-10 | Delo Industrie Klebstoffe Gmbh & Co. Kgaa | Cationically polymerizable flame-retardant masses |
| DE102022114911A1 (en) | 2022-06-14 | 2023-12-14 | Delo Industrie Klebstoffe Gmbh & Co. Kgaa | Method for manufacturing electronic assemblies and wafer-level electronic assembly |
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- 1989-05-29 DE DE68921243T patent/DE68921243T2/en not_active Expired - Fee Related
- 1989-05-29 EP EP89109665A patent/EP0343690B1/en not_active Expired - Lifetime
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| US3542828A (en) * | 1968-02-15 | 1970-11-24 | Koppers Co Inc | Hexafluoroantimonate amine catalysts |
| US3901833A (en) * | 1970-10-23 | 1975-08-26 | Ciba Geigy Corp | Hardenable epoxy resin compositions and process for making the same |
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| US4069055A (en) * | 1974-05-02 | 1978-01-17 | General Electric Company | Photocurable epoxy compositions containing group Va onium salts |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5326827A (en) * | 1990-11-14 | 1994-07-05 | Nippon Paint Co., Ltd. | Heat-curable resin composition containing acrylic polymer having alicyclic epoxide functions |
| US5231186A (en) * | 1991-03-22 | 1993-07-27 | Nippon Paint Co., Ltd. | Quaternary ammonium salts |
| US6019507A (en) * | 1992-11-25 | 2000-02-01 | Terumo Cardiovascular Systems Corporation | Method of making temperature sensor for medical application |
| US6283632B1 (en) | 1992-11-25 | 2001-09-04 | Terumo Cardiovascular Systems Corporation | Method of measuring temperature |
| US6376638B1 (en) | 1998-10-28 | 2002-04-23 | Korea Research Institute Of Chemical Technology | Latent curing agent for epoxy resin initiated by heat and UV-light and epoxy resin composition containing the same and cured epoxy products |
| US6977274B2 (en) * | 1999-01-30 | 2005-12-20 | Korea Research Institute Of Chemical Technology | Epoxy resin curing system containing latent catalytic curing agent causing the expansion of volume |
| US6162950A (en) * | 1999-12-03 | 2000-12-19 | Albemarle Corporation | Preparation of alkali metal tetrakis(F aryl)borates |
| US6169208B1 (en) | 1999-12-03 | 2001-01-02 | Albemarle Corporation | Process for producing a magnesium di[tetrakis(Faryl)borate] and products therefrom |
| US6388138B1 (en) | 1999-12-03 | 2002-05-14 | Albemarle Corporation | Process for producing a magnesium di[tetrakis(Faryl)borate] and products therefrom |
| WO2002006354A1 (en) * | 2000-07-13 | 2002-01-24 | Mcneese State University | Use of deaminatively-generated carbocation as polymerization initiators |
| US6709741B1 (en) * | 2001-09-07 | 2004-03-23 | Taiflex Scientific Co., Ltd. | FPC adhesive of epoxy resin, onium hexafluoroantimonate, nitrile rubber and filler |
| US6773474B2 (en) | 2002-04-19 | 2004-08-10 | 3M Innovative Properties Company | Coated abrasive article |
| US6831200B2 (en) | 2002-10-03 | 2004-12-14 | Albemarle Corporation | Process for producing tetrakis(Faryl)borate salts |
| US20040230075A1 (en) * | 2002-10-03 | 2004-11-18 | Lee John Y. | Process for producing tetrakis(Faryl)borate salts |
| US7087780B2 (en) | 2002-10-03 | 2006-08-08 | Albemarle Corporation | Process for producing tetrakis(Faryl)borate salts |
| US20050215713A1 (en) * | 2004-03-26 | 2005-09-29 | Hessell Edward T | Method of producing a crosslinked coating in the manufacture of integrated circuits |
| US20060110600A1 (en) * | 2004-11-19 | 2006-05-25 | 3M Innovative Properties Company | Anisotropic conductive adhesive composition |
| US20070116961A1 (en) * | 2005-11-23 | 2007-05-24 | 3M Innovative Properties Company | Anisotropic conductive adhesive compositions |
| US20080012124A1 (en) * | 2006-05-16 | 2008-01-17 | Stapleton Russell A | Curable protectant for electronic assemblies |
| US20090311502A1 (en) * | 2006-07-24 | 2009-12-17 | Mccutcheon Jeffrey W | Electrically conductive pressure sensitive adhesives |
| US8846160B2 (en) | 2008-12-05 | 2014-09-30 | 3M Innovative Properties Company | Three-dimensional articles using nonlinear thermal polymerization |
| CN108957952A (en) * | 2017-05-17 | 2018-12-07 | 东京应化工业株式会社 | Solidification compound, cured film, the manufacturing method of display panel and solidfied material |
| WO2023180035A1 (en) | 2022-03-22 | 2023-09-28 | Delo Industrie Klebstoffe Gmbh & Co. Kgaa | Low-temperature-curing compounds based on glycidyl ethers |
| DE102022106647A1 (en) | 2022-03-22 | 2023-09-28 | Delo Industrie Klebstoffe Gmbh & Co. Kgaa | Low-temperature curing compounds based on glycidyl ethers |
Also Published As
| Publication number | Publication date |
|---|---|
| DE68921243D1 (en) | 1995-03-30 |
| EP0343690B1 (en) | 1995-02-22 |
| EP0343690A2 (en) | 1989-11-29 |
| DE68921243T2 (en) | 1995-11-09 |
| CA1329607C (en) | 1994-05-17 |
| EP0343690A3 (en) | 1991-04-24 |
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